Production of solutions of acrylonitrile copolymers and textiles made therefrom



Patented July 15, 1952 PRODUCTION OF SOLUTIONS OF ACRYLO- NITRILE COPOLYMERS: AND TEXTILES MADE THEREFROM Andrew T. Walter,

H. Fremon, Charleston,

South Charleston, andGeorge W. Va., assignors to Union Carbide and Carbon Corporation, a corporation of New York No Drawing. Application May 18,1950,

Serial No. 162,818

11 Claims. 1

This invention relates to new compositions comprising solutions of copolymers of acrylonitrile and Vinyl chloride containing at least 30% of acrylonitrile in the polymer, and to a novel proc ess for .their production'involving the use. of a volatile solvent'boiling well below 100 C. The invention also concerns the production from such solutions of valuable stretched filaments, fibers, yarns, monofils and other textile articles as well as films, sheets, and the like. The solutions can (.01. zoo-32.4)

be used at elevated temperatures as coating, im- I pregnating, sizing and adhesive compositions.

One of the principal objects of the invention is to provide solutions of resinous copolymers of acrylonitrile and vinyl chloride high in acrylonitrile content which are clear and, homogeneous at temperatures below 100 C. and from which the solvent can be removed under commercially practicable conditions without objectionable discolortion or other injury to'the resin article. Another object is to provide a solution of such a resin in a volatile solvent capable of being removed in principal part'from filaments, yarns and other shaped articles made from solutions of the resin in-such solvent under conditions preserving the important physical and chemical properties of the resin article. Another object is the production frorn'such solutions of the aforesaid'resins of stretched filaments, fibersyarns, filaments and the like that aresubstantially free from solvents for said resin boiling above 100 C. and which are dimensionally stable at temperatures up to at least 150 C. Other objects of the invention will be apparent as the following description proceeds.

It is known that certain copolymers of acrylonitrile and vinyl chloride containing between and 55% of acrylonitrile form clear, homogeneous dispersions in acetone, and that stretched filaments and films produced from such dispersions can be rendered dimensionally stable at temperatures around 100 C. and even thereabove by subsequent heat-treatment. Many' important textile applications require that the stretched fibers be dimensionally stable at temperatures as high as 150 Cjto' 200 0., however, and the acryloni'trile-vinyl chloride copolymer fibers of the prior art cannot be used for such applications.

Fibers made of polyacrylonitrile resins generally' are recognized as having high strain-release temperatures. We have found that in the case of the acrylonitrile-vinyl chloride copolymer resins the strain-release temperature of molecularly oriented fibers, filaments and yarns made therefrom increases with the acrylonitrile content of the resin. We also have found that, when dimensional stability at temperatures around 150 C. or higher is a principal requirement of a fiber or yarn made from acrylonitrile-vinyl chloride copolymers, those copolymers contain-- ing at least of the acrylonitrile in the polymer are essential. However, such acrylonitrile-vinyl chloride 00- polymers have very high melt-'vi'scosities and tend to discolor and decompose at high temperatures; and attempts to melt-extrude these resins in the form of fine filaments or thin films have not been successful. The feasibility of fashioning such copolymers into fibers and films is therefore dependent upon their solubility ina practical sense in a commercially availablalow boiling solvent. The solubility in acetone of acrylonitrilevinyl chloride. copolymers containing upto 55% of .acrylonitrile renders them suitable for conversion into, fibers and films. Prior tothis invention, had been found for acrylonitrile-vinyl' chloride copolymers of higher acrylonitrile content.- Solvents thus far proposed for such copolymersand even for polyacrylonitriles have high boilingpoints, are difficultly removable from the spun filaments, and are difiicult to recover in usable form. Efforts to free the spun filaments of such high-boiling solvents by heating cause objectionable; darkening of the filaments, whil efforts to leach such solvents; from the filaments introduce serious solvent-recovery problems.

The present invention is based in important part upon the discovery that acetonitrile, a-l though not 'a solvent at certain acrylonitrile-vmyl chloride copolymers intermediate in composition between polyacryloni trile and the acetone-soluble copolymers of the prior art, is an excellent solvent for such resins at temperatures around 60 C. and above, and that, by forming filaments, fibers and the like from such hot solutions and maintaining such shaped articles attemperatures sufficiently high to prevent precipitation of the resin from thesolution until approximately all of the aceton'itrile: the articles can be has been removed therefrom, converted by known stretching and annealing procedures into strong, tough fibers, yarns and the like having high softening points and strainrelease temperatures, and capable of withstanding substantially higher service temperatures than similar articles made from acetone-soluble acrylonitrile-vinyl chloride copolymers. Acetonitrile offers importantadvantages over high boiling solvents since the former boils at 82 C., is completely miscible with water and the lower aliphatic alcohols, is non-toxic and non-hazardous to personnel under the conditions of use in fiber and film manufacture, and is readily recoverable in pure form from such operations.

While certain acrylonitrile-vinyl chloride resinous copolymers having between around 30% no equallysati-sfactory volatile solventroom temperature for.

rm a soooifi Viscosity Etions selected.

. 3' a and around 75 of acrylonitrile "in the polymer and having specific viscosities within the range from 0.15 to0.7 are soluble in acetonitrile at elevated temperatures around 60C. and are useful with the invention, those copolymers having especial utilityfor the production of commercially useful spun filamentsand yarns have average molecular weights" COI'I'QSPOILding tQ spener.

Since acetonitrile is'not a'solvent at room temf perature for the acetone-insoluble acrylonitrilevinyl chloride ,copolymers herein described, such cific viscosities of between 0.15 'andffbfi, and have i acrylonitrile contents substantially" wholly within the range between about 60% and about 75 the latter varying inversely with the specific Viscosity'of the copolymer, as hereinafter indicated. ".Those resins having acrylonitrile contents within the range between about 60% and about i 71% and specific viscosities of between 0.25 and 0.35; are preferred. The specific viscosities referred t herein are determined at 20 C., using an Qstwald viscosimeter, in accordance withthe I 1 IYiscosity, of a solution of 0.1 gram oi V resinin 50 cc. of dimethyl formamide *1; I viscosity pffdimethyl formamide "The 'specific-viscosity oi the resin is a direct function'of its average molecular weight. The acrylonitrile content of an acetonitrile-soluble copolymer can be; higher, the lower its specific f viscosity. "Thus; acrylonitrile-:vinyl chloride copolymerv resins having acrylonitrile contents above 70% should have sp'ecificviscosities no higher than about,0.3 in order to be acetonitrile soluble at 60 C.-, whereas thoseresins having acrylonitrile contents of 65% :to 70% can have specific viscositiesnp .toj0.6, and those having acrylonitrile contents of'30% to 65% can have specific viscosities even above 0.7.

. llhe. acrylonitrile-vinyl chloridev .coplylffiers useful with this invention a re 1 readily made by anyi of the usual polymerization qprocessesYem ploying peroXy-type catalysts. '1, It is 5 preferred to carryout the polymerization in aqueous emularound 60 or sion.- In making these-emulsions, it'fiscustomary to use emulsifying and wetting agents such as the esters of sulfonated YdicarboXy-lic, acids and the water-soluble salts of alkylatedderivativesof'naphthale'ne sulfonic acids. The, polymerization can be conducted at. room temperature, but'temperatures around 35" C. to 55C.

,are preferred. The polymerization is accelerated by the use of the usual polymerizationfcatae of uniform homogeneous solutions of the resins in acetonitrile without resorting to special techniquesrequired with solvents that are highly activesolvents for the, resin atroom temperature 7 (See G. H. Fremon PatentNo. 2,413,758.)

Dissolution of the resin preferably is effected by heating a mixture of the finely. dividedresin and jacetonitrile in 'a, pressureetight container.

pissolution of. the resin takes place at an elevate'dftemperature whichvarie's'somewhat with the composition and average molecular weight of the resin. Solvationgenerally beginsat about 505C. in the case of resins containing about 130% of acrylonitrile and having specific viscosities in the neighborhood of 0.15 to. 0.20, and at about 75 C. in the case of resins containing around 70% of acrylonitrile and havin specific viscosities around 0.20to 0.25. In, practice, sO'lvation is accomplished in most instances at temperatures around 90C. toj100 C. inpressure-resist ant apparatus, the solvationstep generally requiringfa'n hour or less at such temperatures. lklowevefr, temperatures of 1125" C, or' more can be used,; if desired. Afterj solvation is: complete, solutions of theresinsin acetonitrile are stable at above; but tend to be thiXo tropic'at temperatures around C., while lower temperatures cause the resin to precipitate from solution. Reheatin with-agitation'will render fluid asolution' that has gelled as"a"result""0f cooling to too low a temperature; :Whileth'e gelling tendency --increases with an inoreeso or concentration'of 'resin 'in-fthe solution; yarn has been successfully'spun and-films have been successfully-cast 'frolni solutionsi" ceton itrile ooh;

taiiiing as much ass!) of the resin;

lysts, e. g., the alkali metal persulfates such as potassium persulfate, and the organic perox-- ides such as benzoyl peroxide. If desired," 0.2% to 1% or-more of a higher tertiary aliphatic mercaptan, such as tertiary dodecyl mercaptan, may be present toassist in regulatin the molecular weightof the resin under the reaction. condi- V I When Qmercaptans are used, small additions thereof also maybe made, if desired, during the polymerization. f

A constant ratio of the monomers preferably 7 is maintained in the reaction mixture through} wa ns out the. polymerization by suitable thereto of acrylonitrile as required.

For" theproduction of resinous,acrylonitrile vinyl chloride .copolymers having acrylonitrile contents within the range between and 71%, the weight ratio of monomeric acrylonitrile ,t-o monomeric vinyl chloride in'thel mixture undergoing polymerizationis :maintained within the range betweenabout 1:37 and about 1:1.7,

while for. the production of thosefcopolymers containing around 75% of acrylonitrile an acrylonitrile-vinyl chloride monomer ratioof around 1:13 is required. The average molecular Weights removed from the shaped Theaoetonitrile sollitions ofthis invention may have incorporated thereina small amount} e."g., about 0.25% or more ofthe Weight of the resin, of -'a compound'forstabilizing the resin against decomposition by heatfor bylight'. Suitable compounds are the organ'o metallic tin and lead salts of carboxylic acidsfsuch dibutyl tin maleate.

Such stabilizers'are disclosed in the United States PatentsNos. 2,267,778 alld"2,307,0920f Filaments and yarns can be spun from these acetonitrile solutions at temperatures around o0" (2:80? by either the wet-or dry-spinning pro; cedures, as illustrated herein, Excess solventis 7 filaments by passing thelatter through a current ofair. heated to '120 C.- 200"C., or by immersingthe filamentsin water or anequival-ent non-solvent for the resinwhich is asolventfor acetonitrile. 1 The water can contain' up to'30% of acetonitrile to control the rate of solvent'removal-from the filaments. Generally the yarns are stretched from, to 1,500%

or more at temperatures around 0. 15010 I or'higher to improvetheirphysical properties.

I Under .comparablespinning conditions, .those 7 7 solutions of higher resin content 'yield filaments having more uniform cross-sections than those spun from solutions having-lower resin contents, e, g., '15%'-20% solutions.

' Filaments and fibers wet-spun from acetonitrile solutions of theseresins into water as 'a'coagulant tend to have irregular dog-bone cross-sections even when such solutions have resin-concentrations asyhig-h as 28% 30%. Filaments that are generally round in cross-section and that'have superior yarn qualities are produced when the extruded fibers are coagulated in Water'containing around *10 to 30 p'artsofacetonitrile per 100 parts of the mixture.

. Acetonitr'ile solutions of the acetone-insoluble 'a'crylonitrile vinyl chloride copolymers herein described can be spun into filaments and yarns which, after being stretched and the stretched articles exposed for brief periods to temperatures within the range between 150 'C. and 225 C.

I trile-vinyl chloride copolymers of the'prior art.

In spite of the high proportion of acrylonitrile these copoymers, the films, filaments, fibers and multi-filament yarns made from acetonitrile solutions thereof will not support combustion. Moreover, the stretched filaments and yarns have good wetand dry-tensile strengths and elongation's; and good flexibility, elasticity, resilience, and resistance to water and various chemical agents including acids and dilute alkalies, and to bacterial and fungal growths. The stretched filaments and yarns have wet tenacities upwards of 6 grams per denier and wet elongations of from around'7.5% to 25% or more. The stretched and heat-treated filaments and yarns commonly have shrinkages of less than in oil at 150 C.

The following examples serve to illustrate the invention, but are not intended to limit the scope thereof. In the examples, all partsare given in terms of weight unless otherwise indicated.

Example 1 To a stainless steel autoclave having an agitatorwwere introduced 400 parts of water, 1.5 parts i of sodium dioctyl sulfosuccinate and 0.22 part of tertiary dodecyl mercaptan. A mixture of 73 parts of vinyl chloride and 27 parts of arcylonitrile then was charged to the autoclave, and

a the temperature was raised to 42 C. Potassium persulfate (0.15 part) dissolved in water then was added. The ratio;of acrylonitrile to vinyl chloride monomer in the mixture was maintained approximately uniform by addition of acrylonitrile at frequent intervalsof from 2 to 15. minutes as required. A total 01 33 parts of acrylonitrileand 0.93 part of tertiary dodecylmercaptan wasadded during the polymerization period of'.13.5 hours, after which 49% of the monomers hadbeen convertedtocopolymers. The resin Was recovered by precipitation with an aqueous calciumchloride s0lution,"'washed twice with hot Water, centrifuged,and dried at:65 .C. 7.0.C. This resincontained 66.8% of .acrylonitrileland had a specific viscosityat 20 .C. of 0.25. .It wasinsoluble inacetone; andwas.completelytsoluble in commercial acetonitrile at 50 C. and higher, in concentrations up to at least 30% A portion of the resin was dispersed acetonitrile to form at 75 C. a spinning solution containing approximately 28% of the resin. The resultant solution at 75 C. was forced through a spinneret containing 20 orifices each 0.11 mm. in diameter. The resultant filaments were freed of "excess" solvent in' a counter-current flow of air within a vertical spinningtube maintainedat 180 C.- Th'e filaments were collected on bobbins,

:aged l6 hours at room' temperature,; and then stretched 1.005%" at 140 -C.- Six ends then were,

The resultant .yarn; had :a wet tenacityr ;of 4. 5

grams per denier, "a wetcelon'gation of 14% ,azero --shrinkage inzwateratxl00 .C .,.and a'shrinkage in L steam at 130 .C. of less:than.l.6.%

' .A'nother portion of the stretched, yarnwasrap- 'idly annealedkby iconducting. it continuously through a z'onahe'atd by dry heat to: 190 C. while limiting the shrinkage .of the yarn. to'.16.2%

by take-01f control, .thetimecf exposure iofsthe yarn to the heat bemg substantially 1.11'S6COI1C1S. The resultant yarn had a wet tenacity :of 3.9 grams per denierf a; wet elongation of" 15;7%, zero shrinkages in water at 100 C. and in: oil. at 150 'C.,' respectively, and a shrinkage 'of buti6.9 inoilat20-0C. I T I V. I i amplez The'foll'owing solution was charged to a" glasslined"v autoclave having I a; mechanical agitatortj A mixture of 70 parts of vinyl chloride and 30 conducted for 2.7 hours, ,at which time 27% of the monomer mixture had beenconverteditothe copolymers. During this'tim'e the monomer ratio I of acrylonitrile to vihyl c hloride was maintained approximately uniform in the generalimanner described in Examplel. A total of 43-partsof acrylonitrile and 02 "part of .tertiary dodecyl mercaptanwas added to the autoclave during the polymerization. The resin was recovered and dried in the manner described in Example 1. It contained 62.8%of acrylonitrile-and had aspecific viscosity of 0.3-1 in' dimethyl formamide at 20 C. The resin was insoluble in acetone, but completely solublein' acetonitrile at 60 C. in at A homogeneous clear spinning solutioncon- -taining 28% of the resin inacetonitrile was .made

by heating a mixturei-of the resinand acetonitrile to about 70- C This solution then was dry spun inthe general manner describedimExample 1, forming continuous filaments. The'ztheoretical orifice velocity of the filaments at...the

'spinneret outlet was feet per minute, andthe temperature of the drying air in the spinning cell was C. The resultant filaments were collected, boiled in water 0.5 hour to remove residualacetonitrile, and then were stretched to 600% of their original length during a one-secondgexposure in'steam at C. The stretched yarn had a wet tenacity of 4.7 grams per denier,

a wet elongation of 10.6%, and a shrinkage in boiling water of 13.4%.

A portion of the stretched yarn was heated for three hours'in steam at 135C. while untensioned, yielding a yarn having a wet tenacity of 3.3 grams per denier, a wet elongation of "22.5%, and a zero shrinkage in oil at C.

Another portion of the stretched yarn was passed at highspeed*between=metal blocks main- 'tained' at 180? C. by yne t, while permitting the yarn to shrink 21% during the one-second exposure in this heated zone. The resultant yarn I had a. wet tenacity of BIgramsper deniena wet elongation of, 20.9%, a shrinkage in water at 100 0. 0.1 0.23%, and a shrinkage in on at 200 of of acetonitr'ile with 2 8parts of .a resinous copolymer of acrylonitrile and vinyl. chloride containing 2% of dibutyltin 'maleate based upon the weightof the resin, said' copolymercontaining 67.5%of acrylonitrile and having a specific vis-;

cosity of 0.28 in dimethyl forrnamide at 20' C., and .heating'the mixture 2 hours at 100 Gina 'nitrogen. atmosphere to efiect;.:solution, .After 1 filtering the clear hot solutiongit wasforced through a spinnerette .maintainedat 75E C. and

having 40 orifices each 0.11;:mm. in diameter.

The extruded filaments issued into a, coagulating .bathconsisting of approximately 30 parts of acetonitrile and 70 parts of water maintained at 65 C.,'a'nd were conducted therethrough at a rate permitting a f -second contact with the said bath.: The filaments then .were collected on.,a

bobbin'toformi yarn" at the rate of'150 feet per minute, and wereaged 96: hours in air at room temperature to remoye residual solvent: The resultant yarn was stretched 850% insteam at 145 C. The stretched yarn had a wet tenacity of 2 5.15 grams per denier, a wetelongation of 311%, andashrinkage of, 10.3% in Watl'i t 1oQ2Q.

portion .ofjthe stretchedyarn was heated for 3 hours indryheatat 155f C; while ntensioned. ,The resultant yarnjhadga wet vtenacity of 51.75 :grams perldenienfa' wet; elongation of; 1;3.' 7f7;, a V 3 zero, shrinkage in water at 100 .C. anda shrinkage of 5% in-oiljat' 200 'C. 1

. 'Another portion of the stre hedi air 0f tinuously annealedby passing itthrqu hjaheatking zonema-intained at 2,0,0."- C-.-;by dry heat while permitting the; yarn: to shrink 10%, the time of exposure of the yarn tofsuch heat being- 0.7 sec-.

ond; The resultantyarn had a ;wet tenacity 0f 4.07 grams: per denierya wet -elongation of 114%, and shrinkages-in oilat 150 C.;andat 200 C. of (2%: and 6.8%J,,r sp ct v y-,5

Example};

Employing a" spinning gsomuoii identical with,

that disclosediinrExample 3;;but wherein the dibutyl tin. 'maleate; had been; replaced? ,with r 2% of: dibutyl'atin di(ethylproliylacrylate) ;based upon theweight of, copolymer, yarn was spun, stretched, and annealed ,untensioned' at 155 C.

' under'c'onditions identical with, those recited in Example 3, excepting that the spun yarn was str'etched l,286% in dry heat at 145 C, The

spun yarn had the, following properties:

The the aforesaid a cetonb trile solutions.may be'used either, in th 'stretched .or unstretched condition: for theproduction of staple fiberspr artificial wool-like masses; The

filaments, or-staple fibers made therefrom, are

useful for making felted articles, threads, yarns,

1 etc., either .aloneor in conjunction, with various types of natural fibers .such. as cotton, wool and 1 A homogeneous clear, spinning solution 'was prepared by mixing at room temperature 72 parts silk;- or withother artificial textile fibers such as those made from cellulose acetate, viscose cellulose, nylon, and the vinyl resins such .as polyvinyl chlorides, vinyljchloridevinyl acetate copolymers,

' and acetone-soluble. vinyl .chlorideea'crylonitrile copolymers.

i The new filaments, and staple fibers and yarns made therefrom, are useful for making a wide variety of woven; knitted and braided articles such as in'cl'll'strialiilter fabrics, protectiye pipe covering, electrical in'sulation, protective clothing, bathing suits, hosiery. Land, other ,textile articles. The yarns can he used in pile fabrics, eitheras the baoking or thepilfoi bbthf V In general, ther ace'tonitrile solutions of the resin'are not limitedto use for the production I of textile articles; but can be used for the production atfelevated' temperatures of films, sheets, I and fadhesive, coating andimpregnating compositions and the like ,1". A homogeneous solution comprising a coipolym'er of acrylonitrile and vinyl chloride dissolved in acetonitrile," said copolymer containing between around 30% and around of the acrylonitrile. I 2.' A homogeneous solution comprising a copolymer of acrylonitrile and vinyl chloride dissolved in acetonitrila said copolymer containing between around 30%. and around 75% of the acrylonitrile and having'a'specific viscosity within the range from 0.15 to 0.7. v

3. A homogeneous spinnable solution comprising'a copolymer of acrylonitrile and vinyl chloride dissolved in'acetonitrile, said copolymer containingbetweenaround 60% and around 75% of. the acrylonitrile andhaving a specific viscosity within the range from around 0.15 to around 0.6.

4. A homogeneous spinnable solution comprising a copolymer of acrylonitrile and vinyl chloride dissolved in acietonitrileisaid copolymer containing between around 60% and around 71% of acrylonitrile and having a specific viscosity within therange from around 0.15 to around 0.6.

' 5. Process for preparing homogeneous spinnable solutions of acetone-insoluble copolymers of acrylonitrile and vinyl chloride containing between around 60% and around 75% of the acrylonitrile in the polymer, which comprises dispersing such acopolymer in acetonitrile, and thereafter heating the resultantdispersion to a tem p'ei'ature of .at least. 60-C. with agitation until dissolution. of said copolymer is complete.

6. Process for preparing homogeneous spinnable solutions of acetone-insoluble copolymers' of acrylonitrile and vinyl chloride containing between around 60% andaround 75% of the acrylonitri1e invjthe copolymer, Which'comprises dis-. -p'ersing sucha copolymer in acetonitrile, and

thereafter heating thedispersion to a temperavture withinthe range between around'60 C. and

around C. with agitation until dissolution of said copolymer is complete.

7. A stretched textile article selectedfrom the class consisting of filaments, fibers and 'yarns composed of a resinous acetone-insoluble copolymer of acrylonitrile and vinyl chloride contain-' ing between around 60% and around 75% of the acrylonitrile in the copolymer, said article being substantially free from solvents for said copolymer boiling above 100 C.

8. A stretched textile article selected from the class consisting of filaments, fibers and yarns composed of a resinous acetone-insoluble copolymer of acrylonitrile and vinyl chloride containing between around 60% and around 71% of the acrylonitrile in the copolymer and having a specific viscosity within the range from around 0.15 to around 0.6, said article being substantially free from solvents for said copolymer boil- I ing above 100 C.

9. A stretched textile filament composed of a resinous acetone-insoluble copolymer of acrylonitrile and vinyl chloride containing between around 60% and around 75% of acrylonitrile in the copolymer and having a specific viscosity within the range from 0.15 to 0.6, said filament being approximately round in cross-section and being substantially free from solvents for said copolymer boiling above 100 C.

10. A stretched textile filament composed of a resinous acetone-insoluble copolymer of acrylonitrile and vinyl chloride containing between around 60% and around 75% of acrylonitrile in the copolymer and having a specific viscosity within the range from 0.15 to 0.6, said filament having an irregular dog-bone cross-section and being substantially free from solvents for said copolymer boiling above 100 C.

11. A stretched textile article selected from the class consisting of filamentafibers and yarns composed of a resinous acetone-insoluble copolymer of acrylonitrile and vinyl chloride containing between around and around 71% of the acrylonitrile in the copolymer and having a specific viscosity within the range from around 0.15 to around 0.6, said article being substantially free from solvents for said copolymer boiling above C. and being dimensionally stable at temperatures up to at least C'.

ANDREW T. WALTER. GEORGE H. FREMON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,404,724 Houtz July 23, 1946 2,496,267 Chaney Feb. 7, 1950 2,499,477 Feild Mar. 7, 1950 

1. A HOMOGENEOUS SOLUTION COMPRISING A COPOLYMER OF ACRYLONITRILE AND VINYL CHLORIDE DISSOLVED IN ACETONITRILE, SAID COPOLYMER CONTAINING BETWEEN AROUND 30% AROUND 75% OF THE ACRYLONITRILE. 